Conversion of beta-hydroxy carbonyl species and preparation of amino alcohol precursor using bifunctional catalysts derived from layered double hydroxides

Abstract

Disclosed are methods for conversion of β-hydroxy carbonyl species and preparation of amino alcohol precursor using bifunctional catalysts derived from layer double hydroxides. By the bifunctional catalyst, the abundant basic sites on HTO allow retro-aldol condensation to outpace direct hydrogenation, thus achieving an exceptional selectivity towards a desired product produced through retro-aldol condensation and then hydrogenation. Accordingly, this method exhibits particular utility in the renewable production of N-acetylethanolamine from biomass-derived N-acetyl glucosamine (GlcNAc) without using homogeneous base as a co-catalyst.

What is claimed is: 
     
         1 . A method for conversion of β-hydroxy carbonyl species, the method comprising:
 mixing β-hydroxy carbonyl species with a composite catalyst derived from layered double hydroxides (LDHs), wherein the composite catalyst includes a basic LDHs-derived mixed oxide support and hydrogenation-active species on the basic LDHs-derived mixed oxide support; and 
 catalyzing retro-aldol condensation and then hydrogenation in hydrogen environment using the composite catalyst to complete conversion of the β-hydroxy carbonyl species. 
 
     
     
         2 . The method of  claim 1 , wherein the β-hydroxy carbonyl species includes a nitrogen-containing group. 
     
     
         3 . The method of  claim 1 , wherein the β-hydroxy carbonyl species includes a nitrogen-containing group at Ca position. 
     
     
         4 . The method of  claim 3 , wherein the nitrogen-containing group includes an N-acyl-substituted amino moiety. 
     
     
         5 . The method of  claim 1 , wherein the LDHs are doped M 3+ /N 2+ -LDHs, the M 3+  is a trivalent metal, and the N 2+  is a bivalent metal. 
     
     
         6 . The method of  claim 5 , wherein the hydrogenation-active species are from doping elements of the doped M 3+ /N 2+ -LDHs, and the total molar quantity of the doping elements and the N 2+  is 2 to 4 times that of the M 3+ . 
     
     
         7 . The method of  claim 5 , wherein the M 3+  is Al 3+ , and the N 2+  is Mg 2+ . 
     
     
         8 . The method of  claim 1 , wherein the hydrogenation-active species are nickel nanoparticles. 
     
     
         9 . The method of  claim 1 , wherein the conversion of the β-hydroxy carbonyl species produces an alcohol compound containing an N-acyl-substituted amino moiety and having fewer carbon atoms than the β-hydroxy carbonyl species. 
     
     
         10 . The method of  claim 1 , wherein the β-hydroxy carbonyl species is from a saccharide. 
     
     
         11 . The method of  claim 10 , wherein the saccharide is monosaccharide. 
     
     
         12 . The method of  claim 1 , wherein the conversion of the β-hydroxy carbonyl species proceeds at a temperature in a range of 60° C. to 120° C. 
     
     
         13 . A method for preparing an amino alcohol precursor, comprising:
 providing an amino saccharide; and   mixing the amino saccharide with a composite catalyst derived from layered double hydroxides (LDHs) for conversion of the amino saccharide into the amino alcohol precursor by retro-aldol condensation and then hydrogenation under catalysis of the composite catalyst, wherein the composite catalyst includes a basic LDHs-derived mixed oxide support and hydrogenation-active species on the basic LDHs-derived mixed oxide support.   
     
     
         14 . The method of  claim 13 , wherein the amino saccharide includes an N-acyl-substituted amino moiety. 
     
     
         15 . The method of  claim 13 , wherein the LDHs are doped M 3+ /N 2+  LDHs, the M 3+  is a trivalent metal, and the N 2+  is a bivalent metal. 
     
     
         16 . The method of  claim 15 , wherein the hydrogenation-active species are from doping elements of the doped M 3+ /N 2+ -LDHs, and the total molar quantity of the doping elements and the N 2+  is 2 to 4 times that of the M 3+ . 
     
     
         17 . The method of  claim 15 , wherein the M 3+  is Al 3+ , and the N 2+  is Mg 2+ . 
     
     
         18 . The method of  claim 13 , wherein the hydrogenation-active species are nickel nanoparticles. 
     
     
         19 . The method of  claim 13 , wherein amino alcohol precursor is an alcohol compound containing an N-acyl-substituted amino moiety and having fewer carbon atoms than the amino saccharide. 
     
     
         20 . The method of  claim 13 , wherein the amino saccharide is N-acetyl glucosamine. 
     
     
         21 . The method of  claim 13 , wherein the conversion of the amino saccharide into the amino alcohol precursor proceeds in hydrogen environment at a temperature in a range of 60° C. to 120° C. 
     
     
         22 . The method of  claim 13 , wherein a weight ratio between the amino saccharide and the composite catalyst is 2 or less. 
     
     
         23 . The method of  claim 13 , wherein the amino saccharide is N-acetyl glucosamine, and the amino alcohol precursor is N-acetyl ethanolamine. 
     
     
         24 . The method of  claim 13 , wherein the step of providing the amino saccharide includes depolymerizing chitin biomass.